EP4157937A1 - Composition d'adhésif thermofusible ayant une résistance améliorée au mouillé - Google Patents

Composition d'adhésif thermofusible ayant une résistance améliorée au mouillé

Info

Publication number
EP4157937A1
EP4157937A1 EP21722483.1A EP21722483A EP4157937A1 EP 4157937 A1 EP4157937 A1 EP 4157937A1 EP 21722483 A EP21722483 A EP 21722483A EP 4157937 A1 EP4157937 A1 EP 4157937A1
Authority
EP
European Patent Office
Prior art keywords
styrene
weight
block copolymer
butadiene
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21722483.1A
Other languages
German (de)
English (en)
Inventor
Genta Okazaki
Xin Ye
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bostik SA
Original Assignee
Bostik SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bostik SA filed Critical Bostik SA
Publication of EP4157937A1 publication Critical patent/EP4157937A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2555/00—Personal care
    • B32B2555/02—Diapers or napkins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2571/00—Protective equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B32B5/265—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer
    • B32B5/266—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer next to one or more non-woven fabric layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to a styrene block copolymer-based hot melt adhesive composition and its use for adhering nonwoven materials.
  • Hot melt adhesives are substances which are solid at room temperature and which often comprise neither water nor solvent. They are applied in the molten state after heating to a temperature generally of between 100 and 250°C, most often between 130 and 180°C, and solidify during cooling, thus forming a seal (or adhesive joint) which ensures the attachment of the two substrates to be assembled.
  • Hot melt adhesives are generally provided in the form of compositions which comprise a thermoplastic polymer and optionally a tackifying resin and a plasticizer.
  • Hot melt adhesives are widely used in various applications, such as packaging, bookbinding and woodworking, as they have good stability and do not require the use of solvents. Such adhesives can also be used in nonwoven applications. For example, disposable nonwoven absorbent articles are widely used for infant, young child, incontinent adult and feminine care applications.
  • Typical disposable nonwoven absorbent articles include disposable diapers, training pants, adult incontinent pads and briefs, feminine sanitary napkins or pads, surgical masks. These items aim at receiving and containing body fluids and are usually worn against or in close proximity to the skin.
  • hot melt adhesive compositions are generally used to bond together various substrates of said articles, as they provide rapid bonding compared to other adhesives such as water-based or solvent-based adhesive compositions, which require a drying step of the water or solvent.
  • Hot melt adhesive compositions suitable for this purpose should possess the appropriate bond strength to adhere the substrates involved. More particularly such hot melt adhesives should present a high wet adhesion.
  • wet adhesion is meant the ability to strongly affix to a substrate material in the presence of moist environmental conditions.
  • acid-modified resins or waxes can be added. However, such compounds tend to generate an unpleasant odor and a darker color of the adhesive which can result in a lower quality product.
  • Document US 2018/0100091 relates to a hot melt adhesive comprising a styrenic block copolymer (A) containing a styrene-butadiene-styrene block copolymer (A1 ); and at least one styrenic block copolymer (A4), a tackifier (B); and a plasticizer (C), wherein the hot melt adhesive has a melt viscosity of 6000 mPa.s or lower.
  • Document JP 4436599 relates to a hot melt adhesive comprising a block copolymer, a pressure-sensitive adhesion imparting agent and a plasticizer.
  • the block copolymer contains at least 30 wt% of a styrene-butadiene-styrene block copolymer having a styrene content from 35 to 50 wt.%, a styrene-butadiene diblock content from 50 to 80 wt.% and a viscosity from 20 to 40 mPa.s of a 15 wt.% solution in toluene at 25°C.
  • Document JP 2008239931 relates to a hot melt adhesive containing from 5 to 50% by weight of a styrene-butadiene-styrene triblock copolymer having a content of a styrene-butadiene di-block from 0 to 30% by weight and a content of styrene from 20 to 40% by weight.
  • Document JP 4848184 relates to a hot melt adhesive comprising a thermoplastic block copolymer which is a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound, and a wax modified with a carboxylic acid and/or a carboxylic acid anhydride.
  • Document JP 2015091917 relates to a hot melt adhesive agent containing a thermoplastic block copolymer containing at least one kind of a block copolymer of vinyl aromatic hydrocarbon and a conjugated diene compound, and a hydrogenated product thereof and an acid modified petroleum resin manufactured by acid modification by unsaturated carboxylic acid or anhydride thereof.
  • Document WO 2015/002308 relates to a hot melt adhesive composition
  • a thermoplastic block copolymer (A) that comprises at least one component selected from the group consisting of a styrene-isoprene-styrene block copolymer and a styrene-butadiene/butylene-styrene block copolymer; a liquid rubber (B) having a carboxyl group and/or a carboxylic acid anhydride group in the molecule; and an adhesiveness-imparting resin (C).
  • Document WO 2015/125546 relates to a hot melt adhesive composition comprising a thermoplastic polymer and a tackifier, wherein the tackifier includes an acid-modified tackifier.
  • Document WO 2018/074070 relates to a hot melt adhesive composition that comprises a thermoplastic polymer, a tackifier, and a softener, wherein the softener includes an acid-modified oil modified by at least one of carboxylic acid and carboxylic acid anhydride.
  • It is a first object of the invention to provide a hot melt adhesive composition comprising a polymer component, the polymer component comprising: at least one styrene-butadiene-styrene block copolymer P having: a styrene content from 35 to 50 % by weight; a styrene-butadiene diblock content from 50 to 80 % by weight; and a viscosity of a 15 % by weight toluene solution at 25°C of 20 to 40 mPa.s; at least one styrene block copolymer other than a styrene-butadiene- styrene block copolymer; wherein said styrene-butadiene-styrene block copolymer P is at a content from 10 to 40 % by weight relative to the total weight of the polymer component.
  • the styrene-butadiene-styrene block copolymer P is at a content from 10 to 35 % by weight, preferably from 10 to 30 % by weight, more preferably from 10 to 28 % by weight and more preferably from 10 to 25 % by weight relative to the total weight of the polymer component.
  • the at least one styrene block copolymer other than a styrene-butadiene-styrene block copolymer is chosen from styrene- butadiene, styrene-isoprene-styrene, styrene-isoprene, styrene-isoprene- butadiene-styrene, styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene propylene, styrene-ethylene-ethylene-propylene-styrene copolymers, and mixtures thereof.
  • the at least one styrene block copolymer other than a styrene-butadiene-styrene is a styrene-isoprene-styrene block copolymer.
  • the at least one styrene block copolymer other than a styrene-butadiene-styrene is at a content from 0.1 to 60 % by weight, preferably from 1 to 30 % by weight, more preferably from 2 to 20 % by weight and even more preferably from 5 to 15 % by weight relative to the total weight of the polymer component.
  • the polymer component comprises: from 40 to 85 wt.%, and preferably from 50 to 80 wt.%, of at least one styrene-butadiene-styrene block copolymer different from the styrene-butadiene-styrene block copolymer P; from 1 to 20 wt.%, preferably from 5 to 15 wt.% of a styrene-isoprene- styrene block copolymer.
  • the composition is devoid of a resin, wax or oil modified by an unsaturated polycarboxylic acid, anhydride or ester.
  • the composition has a viscosity from 1 000 to 30 000 mPa.s and preferably from 5 000 to 20 000 mPa.s at a temperature of 120°C.
  • the total amount of polymer component is from 10 % to 80 % by weight, more preferably from 15 % to 45 % by weight, and even more preferably from 15 % to 35 % by weight, relative to the total weight of the hot melt adhesive composition.
  • the composition further comprises from 45 to 75 % of a tackifying resin relative to the total weight of the composition, and/or from 5 to 25 % of a plasticizer relative to the total weight of the composition, and/or from 0.1 to 5 % of a stabilizer relative to the total weight of the composition, and/or from 0 to 30 % of a wax relative to the total weight of the composition.
  • the invention also relates to the use of the composition described above, as an adhesive for bonding two substrates together, or as a coating on the surface of a substrate.
  • the invention also relates to an article comprising at least one interior or exterior surface coated with the hot melt adhesive composition described above.
  • the interior or exterior surface is a nonwoven fabric.
  • the article is chosen from a disposable diaper, disposable training pants, a feminine sanitary napkin, an adsorbent pad, a surgical mask, and a surgical coat.
  • the present invention makes it possible to address the need mentioned above.
  • the invention provides a hot melt adhesive composition which provides good adhesion, notably a high wet bonding strength in particular in nonwoven material-based products.
  • thermoplastic adhesive composition of the present invention affords high wet adhesion and also high dry adhesion which makes it possible to provide non-woven-based articles of good quality.
  • the composition of the present invention can be devoid of an acid-modified resin, wax or oil.
  • problems related to an unpleasant odor and/or a darker color of the adhesive can be limited.
  • the hot melt adhesive composition of the present invention comprises a polymer component and may also comprise other additional components.
  • hot melf is used herein to describe that the adhesive composition requires to be heated at at least 120°C, and preferably at least 140°C, to be applied on a substrate.
  • the hot melt adhesive composition is thus solid at 23°C.
  • the polymer component of the hot melt adhesive composition comprises at least one styrene-butadiene-styrene (SBS) block copolymer P having the following properties: a styrene content from 35 to 50 % by weight; a styrene- butadiene diblock content from 50 to 80 % by weight; and a viscosity of a 15 % by weight toluene solution at 25°C of 20 to 40 mPa.s.
  • SBS styrene-butadiene-styrene
  • the " styrene content' refers to the ratio of the styrene block contained in the SBS block copolymer.
  • the styrene content is from 35 to 50 % by weight, more preferably from 35 to 45 % by weight, and particularly preferably from 40 to 45 % by weight.
  • the holding power (cohesion) of the hotmelt adhesive itself can be reduced, and when the styrene content rate exceeds 50 % by weight, the tackiness of the hotmelt adhesive itself can be reduced.
  • the " diblock content" refers to the ratio of the styrene-butadiene diblock copolymer in the SBS block copolymer.
  • the diblock content is from 50 to 80 % by weight, more preferably 55 to 75 % by weight, and particularly preferably from 60 to 70 % by weight.
  • the diblock content is less than 50 % by weight, the tackiness can be poor.
  • the hotmelt adhesive tends to be detached from the substrate at its interface because of poor tackiness.
  • the diblock content exceeds 80 % by weight, the holding power (cohesion) and the adhesion at a high temperature of the hotmelt adhesive can be reduced.
  • the "viscosity of a 15 % by weight toluene solution at 25°C' refers to the viscosity of a solution having a concentration of 15 % by weight using toluene as a solvent at 25°C.
  • the viscosity is measured by using a Brookfield viscometer.
  • the viscosity of a 15 wt% toluene solution of the SBS block copolymer at 25°C is from 20 to 40 mPa.s, and more preferably from 20 to 35 mPa.s. When this viscosity is less than 20 mPa.s, the molecular weight of the SBS block copolymer is low.
  • the polymer is hardly solidified when producing the SBS block copolymer, that is, the softening point can be low when it is formed into a hot melt adhesive, and blocking can be caused in its production line or caused by cold flow after being molded.
  • this viscosity is more than 40 mPa.s, the viscosity of the hot melt adhesive itself is high and it can hardly be applied. In particular, non-contact application can be difficult at a low temperature.
  • the SBS block copolymer P may be hydrogenated or not. According to preferred embodiments, the SBS block copolymer is not hydrogenated.
  • the SBS block copolymer P has a melt index (MFI) of less than 150 grams/10 minutes, more preferably less than 100 grams/10 minutes, and more preferably less than 60 grams/10.
  • MFI melt index
  • the MFI may be measured by ASTMD 1238 or IS01133 at 190°C or 200°C (preferably 190°C) under a load of 5 kg.
  • the SBS block copolymer P is present in an amount from 10 to 40 % by weight, relative to the total weight of the polymer component.
  • the SBS block copolymer may be present in an amount from 10 to 35% by weight, preferably from 10 to 30% by weight, more preferably from 10 to 28 % by weight and more preferably from 10 to 25 % by weight relative to the total weight of the polymer component.
  • the SBS block copolymer P may be present in an amount from 10 to 15 % by weight, or from 15 to 20 % by weight, or from 20 to 25 % by weight, or from 25 to 30 % by weight, or from 30 to 35 % by weight, or from 35 to 40 % by weight relative to the total weight of the polymer component.
  • the hot melt adhesive composition and more particularly the polymer component comprises one SBS block copolymer P as described above.
  • the hot melt adhesive composition and more particularly the polymer component comprises more than one SBS block copolymer P as described above, for example, two, or three, or four, or five or more than five SBS block copolymer P as described above.
  • the polymer component may also comprise another SBS block copolymer, not according to the above definition.
  • the polymer component may comprise a SBS block copolymer which has a styrene content other than 35 to 50 % by weight, and/or a styrene-butadiene diblock content other than 50 to 80 % by weight, and/or a viscosity of a 15 % by weight toluene solution at 25°C other than 20 to 40 mPa.s.
  • This SBS block copolymer different from the copolymer P may preferably be present in the polymer component in an amount from 40 to 85 %, and more preferably from 50 to 80 % by weight relative to the total weight of the polymer component.
  • the polymer component of the hot melt adhesive composition does not comprise any SBS block copolymer other than the SBS block copolymer(s) P defined and described above.
  • the polymer component also comprises at least one styrene block copolymer other than a styrene-butadiene-styrene block copolymer.
  • SBC styrene block copolymers
  • SBC styrene block copolymers
  • SBS styrene-butadiene
  • SI styrene-isoprene-styrene
  • SI styrene-isoprene
  • SIBS styrene-isoprene-butadiene-styrene
  • SEBS styrene-ethylene butylene- styrene
  • SEB styrene-ethylene-propylene- styrene
  • SEPS styrene-ethylene-propylene- styrene
  • composition according to the invention makes it possible to improve the softness of the hot-melt adhesive composition and also its adhesion, notably at low temperatures.
  • the styrene block copolymer other than a SBS block copolymer comprises a SIS block copolymer.
  • only one styrene block copolymer other than a SBS block copolymer is present in the polymer component of the hot melt adhesive composition of the present invention. It is preferably a SIS block copolymer.
  • more than one (for example, two, or three, or four, or five or more than five) styrene block copolymers other than a SBS block copolymer are present in the polymer component of the hot melt adhesive composition of the present invention.
  • the styrene content of the styrene block copolymer other than a SBS block copolymer may for example be from 5 to 50 % by weight, more preferably from 10 to 40 % by weight, and particularly preferably from 10 to 30 % by weight.
  • the viscosity of a 15 wt% toluene solution of styrene block copolymer other than a SBS block copolymer at 25°C is from 50 to 2 000 mPa.s, and more preferably from 50 to 1 000 mPa.s. The viscosity is measured by using a Brookfield viscometer.
  • the styrene block copolymer other than a SBS block copolymer may preferably be present in an amount from 0,1 to 60% by weight, preferably from 1 to 30 % by weight, more preferably from 2 to 20 % by weight, and even more preferably from 5 to 15 % by weight relative to the total weight of the polymer component.
  • the total amount of polymer component used according to the invention preferably ranges from 10 % to 80 % by weight, more preferably from 15 % to 45 % by weight, and even more preferably from 15 % to 35 % by weight, relative to the total weight of the hot melt adhesive composition.
  • the hot melt adhesive composition may comprise one or more additional components.
  • additional components can be chosen from a tackifying resin, a plasticizer, a wax, a stabilizer and other additives.
  • the hot melt adhesive composition preferably comprises a tackifying resin.
  • the tackifying resin can be present in the hot melt adhesive composition at a content of 45 to 75 % by weight, and preferably from 50 to 70 % by weight relative to the total weight of the hot melt adhesive composition.
  • tackifying resins or tackifiers which are used in the hot melt adhesives of the present invention are those which are compatible with the polymers and extend adhesive properties and improve specific adhesion.
  • tackifying resin or "tackifier 1 ' include:
  • Polyterpene resins having a softening point from 95°C to 140°C the latter polyterpene resins generally resulting from the polymerization of terpene hydrocarbons, such as the mono-terpene known as pinene, in the presence of Friedel-Crafts catalysts at moderately low temperatures; the hydrogenated polyterpene resins are also included;
  • Natural and modified rosin such as, for example, gun rosin, wood rosin, tail-oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin and polymerized rosin;
  • Glycerol and pentaerythritol esters of natural and modified rosin such as, for example, the glycerol ester of pale wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of pale wood rosin, the pentaerythritol ester of hydrogenated rosin, the pentaerythritol ester of tail-oil rosin, and the phenolic modified pentaerythritol ester of rosin;
  • natural and modified rosin such as, for example, the glycerol ester of pale wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of pale wood rosin, the pentaerythritol ester of hydrogenated rosin,
  • Phenolic-modified terpene resins such as for example, the resin product resulting from the condensation in an acidic medium of a terpene and a phenol.
  • the resin is not modified by an unsaturated polycarboxylic acid, anhydride or ester (in other words, the composition does not comprise any resin modified by an unsaturated polycarboxylic acid, anhydride or ester).
  • Mixtures of two or more of the above described tackifying resins may also be used.
  • Tackifying resins which are useful for the present invention can include polar tackifying resins.
  • the choice of available polar tackifying resins is limited in view of the fact that many of the polar resins appear only partially compatible with polyolefin polymers.
  • the tackifying resins can be selected from any of the nonpolar types, which are commercially available.
  • One class of preferred resins are aliphatic petroleum hydrocarbon resins, examples of which are based on C5 olefins.
  • Most preferred are nonpolar products which are hydrogenated di-cyclo-pentadiene (DCPD) based or aromatically modified derivatives thereof with softening points above 95°C.
  • DCPD hydrogenated di-cyclo-pentadiene
  • examples of such resins are Escorez 5340, Escorez 5400 and Escorez 5600 sold by ExxonMobil Chemical company.
  • the tackifying resin should have a Ring and Ball softening point (measured by ASTM E28) of at least 95°C and preferably from 95°C to 140°C.
  • the tackifying resin should be substantially aliphatic to insure compatibility between the resin and the polyolefin polymers.
  • a plasticizer is preferably present in the hot melt adhesive composition. More particularly, a solid or liquid plasticizer can be present in the composition of the present invention.
  • the plasticizer is not modified by an unsaturated polycarboxylic acid, anhydride or ester (in other words, the composition does not comprise any plasticizer modified by an unsaturated polycarboxylic acid, anhydride or ester).
  • the plasticizer may be present in the hot melt adhesive composition at a content from 5 to 25 % by weight, and preferably from 10 to 23 % by weight relative to the weight of the composition.
  • a suitable plasticizer may be selected from the group which includes the usual plasticizing oils, such as mineral oils, but also olefin oligomers and low molecular weight polymers, as well as vegetable and animal oils and derivatives of such oils.
  • the petroleum derived oils which may be employed are relatively high boiling materials containing only a minor proportion of aromatic hydrocarbons.
  • the oligomers may be polypropylenes, polybutenes, hydrogenated polyisoprenes, hydrogenated polybutadienes, or the like having an average molecular weight between 350 and 10,000.
  • Suitable vegetable and animal oils include glycerol esters of the usual fatty acids and polymerization products thereof.
  • the plasticizers that are useful in the present invention can be any number of different plasticizers but mineral oils and liquid polybutenes having an average molecular weight less than 5,000 are particularly advantageous.
  • plasticizers are used to lower the viscosity of the overall hot melt adhesive composition without substantially decreasing the adhesive strength and/or service temperature of the adhesive composition as well as to extend the open time and to improve flexibility of the composition
  • the composition according to the present invention also preferably includes at least one stabilizer.
  • the stabilizer may be present in the hot melt adhesive composition at a content from 0.1 to 5 % and preferably from 0.5 to 3 % by weight relative to the weight of the composition.
  • the stabilizers which are useful in the hot melt adhesive composition of the present invention are incorporated to help protect the polymers noted above, and thereby the total adhesive system from the effects of thermal and oxidative degradation which normally occurs during the manufacture and application of the adhesive, as well as in the ordinary exposure of the final product to the ambient environment.
  • hindered phenols include:
  • Especially preferred as a stabilizer is pentaerythritol tetrakis-3(3,5-di-tert- butyl-4-hydroxyphenol) propionate.
  • the performance of these stabilizers may be further enhanced by utilizing, in conjunction therewith; (1 ) synergists such as, for example, thiodipropionate esters and phosphites; examples of these include dialuryl thiodipropionate (DLTDP) and tris(nonylphenyl)phosphite (TNPP), respectively; and (2) chelating agents and metal deactivators as, for example, ethylenediaminetetraacitic acid, salts thereof and disalicylalpropylenediimine.
  • synergists such as, for example, thiodipropionate esters and phosphites; examples of these include dialuryl thiodipropionate (DLTDP) and tris(nonylphenyl)phosphite (TNPP), respectively
  • DLTDP dialuryl thiodipropionate
  • TNPP tris(nonylphenyl)phosphite
  • composition according to the present invention may further include at least one wax.
  • the wax may be present in the hot melt adhesive composition at a content from 0 to 30 % and preferably from 0.5 to 3 % by weight relative to the weight of the composition.
  • wax makes it possible to reduce the melt viscosity of the hot melt adhesive without appreciably decreasing its adhesive bonding characteristics.
  • These waxes are also used to reduce the open time, or set-up time of the composition without affecting the temperature performance.
  • low molecular weight that is, number average molecular weight (Mn) from 100 to 6000 g/mol, polyethylene wax having a hardness value, as determined by ASTM method D-1321 , from 0.1 to 120 and ASTM softening points from 65°C to 140°C;
  • metallocene catalyzed wax or single-site catalyzed wax like for example those described in US 4,914,253, US 6,319,979, WO 97/33921 or WO 98/03603,
  • polyolefin wax refers to those polymeric or long-chain entities comprised of olefinic monomer units. These materials are commercially available from Westlake Chemical Co. under the trade name " Epolene ".
  • the wax is not modified by an unsaturated polycarboxylic acid, anhydride or ester (in other words, the composition does not comprise any wax modified by an unsaturated polycarboxylic acid, anhydride or ester).
  • the wax materials used have a Ring and Ball softening point from 93°C to 177°C.
  • each of these waxes is solid at room temperature.
  • Other useful substances include hydrogenated animal, fish and vegetable fats and oils such as hydrogenated tallow, lard, soy oil, cottonseed oil, castor oil, menhadin oil, cod liver oil, and the like, and which are solid at ambient temperature by virtue of their being hydrogenated, have also been found to be useful with respect to functioning as a wax material equivalent. These hydrogenated materials are often referred to in the adhesives industry as “animal or vegetable waxes”.
  • auxiliary additives may be incorporated in the hot melt adhesive composition, in order to modify one or more physical properties of the composition.
  • These auxiliary additives may be present in the hot melt adhesive composition at a total amount from 0.01 to 3 % by weight relative to the weight of the composition.
  • Such additives may include, for example, inert colorants such as titanium dioxide as well as fillers, surfactants, other types of polymers, crosslinking agents, nucleating agents, reactive compounds, fire-retardant mineral or organic agents, ultraviolet (UV) or infrared (IR) light absorbing agents, and UV or IR fluorescing agents.
  • Typical fillers include talc, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass microspheres, ceramic microspheres, thermoplastic microspheres, baryte and wood flour. These optional auxiliary additives are well known in this art.
  • the composition of the present invention is devoid of an acid-modified component.
  • Such compounds may include for example a wax, a resin (for example a petroleum or a tackifier resin), a softening agent, an oil, a plasticizer or a rubber.
  • the composition of the present invention is devoid of a component modified by an unsaturated polycarboxylic acid, anhydride or ester (therefore comprising one or more acidic groups).
  • polycarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid and polycarboxylic acid.
  • the present invention makes it possible to obtain a composition which is devoid of such compounds and maintains a high wet adhesion and also a good dry adhesion.
  • the hot melt adhesive composition may comprise from 10 to 40 % by weight of the SBS block copolymer P relative to the total weight of the polymer component, and from 0,1 to 30 % by weight of a styrene block copolymer other than the SBS block copolymer P (for example a SIS block copolymer) relative to the total weight of the polymer component and from 40 to 85 % by weight of a SBS block copolymer different from the copolymer P relative to the total weight of the polymer component.
  • a styrene block copolymer other than the SBS block copolymer P for example a SIS block copolymer
  • the composition of the present invention may have a viscosity from 1 000 to 30 000 mPa.s and preferably from 5 000 to 20 000 mPa.s at a temperature of 120°C.
  • the viscosity can be measured according to the ASTM D3236 standard in a Brookfield RVT viscometer (spindle #27).
  • the composition of the present invention may have a softening point from 65 to 100°C, and preferably from 70 to 85°C. The softening point can be measured according to the ASTM E-28 standard.
  • the composition of the present invention makes it possible to achieve an average wet peel strength equal to or higher than 0.4 N, preferably equal to or higher than 0.6 N, and preferably equal to or higher than 0.8 N. Wet peel strength is measured as indicated below:
  • the composition is first heated at a temperature from 140 to 160°C and is then applied to a primary substrate which is a hydrophilic spunbond non-woven fabric at 3 g/m 2 coating weight by Omega application with 0.3 seconds open time and 0.01 MPa compression at the nip rolls.
  • the pattern of the hot-melt adhesive composition has a width of 15 mm.
  • a secondary substrate hydrophilic spunbond non-woven fabric is then laminated with the primary substrate comprising the composition.
  • the laminate is then stored at 23°C under an atmosphere of 50 % relative humidity for 24 hours to cool and solidify the hot melt adhesive.
  • the laminate is then cut in order to obtain test specimens having a width of 40 mm and a length of 75 mm.
  • the test specimen is immersed in water at 23°C for 5 sec and the wet test specimen is obtained by wiping off water. After that, the T-peel test is performed by pulling apart the wet test specimen at a rate of 300 mm/min at 23°C and the wet peel strength is measured.
  • composition of the present invention makes it possible to achieve an average dry peel strength equal to or higher than 0.2 N, preferably equal to or higher than 0.4 N, and preferably equal to or higher than 0.6 N. Dry peel strength is measured as indicated below:
  • the composition is first heated at a temperature from 140 to 160°C and is then applied to a primary substrate which is a hydrophilic spunbond non-woven fabric at 3 g/m 2 coating weight by Omega application with 0.3 seconds open time and 0.01 MPa compression at the nip rolls.
  • the pattern of the hot-melt adhesive composition has a width of 15 mm.
  • a secondary substrate hydrophilic spunbond non-woven fabric is then laminated with the primary substrate comprising the composition.
  • the laminate is then stored at 23°C under an atmosphere of 50 % relative humidity for 24 hours to cool and solidify the hot melt adhesive.
  • the laminate is then cut in order to obtain test specimens having a width of 40 mm and a length of 75 mm.
  • the T-peel test is performed by pulling apart the test specimen at a rate of 300 mm/min at 23°C and dry peel strength is measured.
  • the invention also relates to the use of the hot melt adhesive composition as described above, for coating a substrate or for bonding two substrates together.
  • Each substrate to be coated or bonded may comprise a film, nonwoven material or woven material. It may comprise absorbent fluff, super absorbent polymer (SAP), composite material, plastics which may be elastomeric or non- elastomeric, for example styrene block copolymers (SBC), polyurethane, and polyolefin, and any mixture thereof.
  • the substrate is a nonwoven fabric.
  • the process of manufacturing an assembly product may comprise:
  • step (i) of heating the hot melt adhesive composition according to the invention e.g. at a temperature ranging from 120°C to 180°C, for at least a period of time long enough to render the hot melt adhesive composition liquid enough to be applied on a substrate (for example at least two hours), then
  • the invention also relates to the use of the hot melt adhesive composition as described above, for bonding two substrates.
  • the substrates may be different or of the same nature, with various forms (layer or film, strands, fluff).
  • At least one of the substrates, and more preferably both substrates are nonwoven fabrics.
  • the invention relates to an article comprising at least one interior or exterior surface coated with the hot melt adhesive composition as described above.
  • the present invention relates to an assembly product comprising at least two substrates bonded by at least one hot melt adhesive composition according to the invention.
  • coated surface and the bonded substrates may be as described above.
  • the hot melt adhesive composition according to the invention may be used as the laminating adhesive to bind a plurality of substrate layers for example to manufacture toilet tissues, paper towels, wipes and other consumer products, particularly absorbent articles such as disposable hygiene products, and more particularly disposable diapers.
  • the assembly product according to the invention may be a multilayer product comprising at least two layers of substrate(s) bonded by at least one hot melt adhesive composition according to the invention.
  • the at least two layers of substrate(s) may be joined adhesively by a layer of the hot melt adhesive composition according to the invention, sandwiched between the two layers of substrate (s).
  • the at least two layers of substrate(s) may be adhesively joined by spots of the hot melt adhesive composition according to the invention.
  • the article/assembly product is a disposable nonwoven absorbent article. Mention can be made of disposable diapers, disposable training pants, disposable adult incontinent pads or briefs and disposable feminine sanitary napkins or pads, surgical masks and surgical coats.
  • compositions A to H are according to the invention while compositions I to N are comparative compositions.
  • the compositions A to N comprise some of the following compounds:
  • SBS1 LCY GlobalpreneTM 3545 available from LCY. Linear SBS having a styrene content of 45 %, a diblock content of 65 % and a viscosity of a 15 % by weight toluene solution at 25°C of 30 mPa.s (corresponding to a block copolymer P).
  • SBS2 Taipol ® 4270 available from TSRC.
  • Linear SBS having a styrene content of 37 %, a diblock content of 70 % and an MFI of 20.5 g/10 min (190°Cx5 kg) (corresponding to a block copolymer other than P).
  • This polymer has a viscosity of a 15 % by weight toluene solution at 25°C of 43.5 mPa.s. The viscosity measurement was done with Spindle No.21 .
  • SBS3 AsapreneTM T-439 available from Asahi. Linear SBS having a styrene content of 45 %, a diblock content of 65 % and a viscosity of a 15 % by weight toluene solution at 25°C of 25 mPa.s (corresponding to a block copolymer P).
  • SBS4 AsapreneTM T-438 available from Asahi. Linear SBS having a styrene content of 35 %, a diblock content of 70 % and a viscosity of a 15 % by weight toluene solution at 25°C of 47.5 mPa.s (corresponding to a block copolymer other than P).
  • SIS SIS 1126 available from Sinopec. Linear SIS having a styrene content of 16 %, a diblock content of 50 % and a viscosity of a 25 % by weight toluene solution at 25°C of 900 mPa.s.
  • R1 Quintone ® D295 available from Zeon. Acid-modified non- hydrogenated petroleum resin. This resin is modified with maleic acid and has a softening point of 94°C and an acid value of 8.0 mg KOH / g.
  • R2 Non-acid modified hydrogenated resin
  • Arkon M-100 Partially Hydrogenated C9 petroleum resin with a softening point of 100°C available from Arakawa Chemical;
  • R3 Non-acid modified hydrogenated resin
  • I marv P-100 Fully hydrogenated DCPD/C9 petroleum resin with a softening point of 100°C available from Idemitsu Kosan;
  • R5 Non-acid modified hydrogenated resin
  • HD1100 Fully Hydrogenated DCPD petroleum resin with a softening point of 100°C available from Luhua;
  • R6 Non-acid modified hydrogenated resin
  • FM100 Partially
  • R7 Non-acid modified hydrogenated resin
  • HB103 Hydrogenated DCPD/C9 petroleum resin with a softening point of 100°C available from JXTG;
  • P1 paraffinic oil plasticizer
  • Diana Fresia S32 available from Idemistu P2 paraffinic oil plasticizer
  • Apar Poweroil H350 available from Apar.
  • P3 naphthenic oil plasticizer.
  • N4010 available from Karamay.
  • A1 Antioxidant Evernox ® 10 available from Everspring.
  • compositions A to N were prepared by placing the components listed in the table above into a jacketed mixing kettle equipped with a heater and a stirrer, and then mixed while heating at 170°C for 120 min under vacuum to remove any entrapped air.
  • the viscosity of the compositions A to N was measured according to the ASTM D3236 standard in a Brookfield RVT viscometer.
  • the softening point of the compositions A to N was measured according to the ASTM E-28 standard. The results are disclosed in the table below:
  • compositions according to the present invention make it possible to achieve at the same time a high wet peel strength and a good dry peel strength. Furthermore, even when the composition is devoid of an acid-modified compound (A, B, E, G, H), a high wet peel strength and a dry peel strength can still be achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition d'adhésif thermofusible comprenant un constituant polymère, le constituant polymère comprenant au moins un copolymère P à blocs styrène-butadiène-styrène ayant une teneur en styrène de 35 à 50 % en poids ; une teneur en diblocs styrène-butadiène de 50 à 80 % en poids ; et une viscosité d'une solution dans le toluène à 15 % en poids à 25 °C de 20 à 40 mPa.s, et au moins un copolymère à blocs styrène autre qu'un copolymère à blocs styrène-butadiène-styrène, ledit copolymère P à blocs styrène-butadiène-styrène étant présent en une quantité de 10 à 40 % en poids par rapport au poids total du constituant polymère. L'invention concerne également l'utilisation de ladite composition comme adhésif pour coller deux substrats, et des articles comprenant au moins une surface intérieure ou extérieure revêtues de ladite composition.
EP21722483.1A 2020-05-27 2021-05-04 Composition d'adhésif thermofusible ayant une résistance améliorée au mouillé Pending EP4157937A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20176828.0A EP3916053A1 (fr) 2020-05-27 2020-05-27 Composition adhésive thermofusible ayant une force de collage humide améliorée
PCT/EP2021/061660 WO2021239404A1 (fr) 2020-05-27 2021-05-04 Composition d'adhésif thermofusible ayant une résistance améliorée au mouillé

Publications (1)

Publication Number Publication Date
EP4157937A1 true EP4157937A1 (fr) 2023-04-05

Family

ID=70861331

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20176828.0A Withdrawn EP3916053A1 (fr) 2020-05-27 2020-05-27 Composition adhésive thermofusible ayant une force de collage humide améliorée
EP21722483.1A Pending EP4157937A1 (fr) 2020-05-27 2021-05-04 Composition d'adhésif thermofusible ayant une résistance améliorée au mouillé

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20176828.0A Withdrawn EP3916053A1 (fr) 2020-05-27 2020-05-27 Composition adhésive thermofusible ayant une force de collage humide améliorée

Country Status (6)

Country Link
US (1) US20230235203A1 (fr)
EP (2) EP3916053A1 (fr)
JP (1) JP2023526969A (fr)
CN (1) CN115551940A (fr)
MX (1) MX2022014547A (fr)
WO (1) WO2021239404A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114231224B (zh) * 2021-12-24 2023-03-21 恒河材料科技股份有限公司 一种适用于evoh粘接的羧基官能化sibs弹性体及其制备方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914253A (en) 1988-11-04 1990-04-03 Exxon Chemical Patents Inc. Method for preparing polyethylene wax by gas phase polymerization
ID17196A (id) 1996-03-14 1997-12-11 Dow Chemical Co Bahan-bahan perekat yang mengandung polimer-polimer olefin
BR9710552A (pt) 1996-07-22 1999-08-17 Dow Chemical Co Adesivo de fusÆo a quente embalagem artigo para embalagem e processo de polimeriza-Æo
JP4217449B2 (ja) * 2002-09-26 2009-02-04 ヘンケルテクノロジーズジャパン株式会社 ホットメルト型粘着組成物
JP4436599B2 (ja) 2002-10-15 2010-03-24 ヘンケルジャパン株式会社 ホットメルト接着剤及びそれを用いた使い捨て製品
JP4848184B2 (ja) 2005-12-26 2011-12-28 ヘンケルジャパン株式会社 ホットメルト接着剤及び使い捨て製品
JP2008239931A (ja) 2007-03-29 2008-10-09 Sekisui Fuller Co Ltd ホットメルト接着剤および使い捨て製品
JP6023001B2 (ja) 2013-05-22 2016-11-09 ヘンケルジャパン株式会社 ホットメルト接着剤
JP5404958B1 (ja) 2013-07-05 2014-02-05 積水フーラー株式会社 ホットメルト接着剤組成物及びこれを用いてなる吸水性物品
JP5539599B1 (ja) 2013-09-30 2014-07-02 積水フーラー株式会社 ホットメルト接着剤及びこれを用いてなる使い捨て製品
WO2015125546A1 (fr) 2014-02-21 2015-08-27 株式会社Moresco Adhésif thermofusible
JP6707529B2 (ja) 2014-09-09 2020-06-10 エイチ．ビー．フラー カンパニー 弾性ホットメルト接着剤組成物及びそれと共に製造される弾性複合材料
CN107532053A (zh) 2015-04-23 2018-01-02 积水富乐株式会社 热熔胶粘剂和使用其的一次性产品
WO2018074070A1 (fr) 2016-10-18 2018-04-26 株式会社Moresco Adhésif thermofusible
EP3339390A1 (fr) * 2016-12-21 2018-06-27 Bostik Sa Composition adhésive thermofusible pour des accessoires élastiques
KR102397831B1 (ko) * 2017-12-27 2022-05-12 주식회사 엘지화학 핫 멜트 접착제 조성물

Also Published As

Publication number Publication date
MX2022014547A (es) 2022-12-15
WO2021239404A1 (fr) 2021-12-02
CN115551940A (zh) 2022-12-30
EP3916053A1 (fr) 2021-12-01
JP2023526969A (ja) 2023-06-26
US20230235203A1 (en) 2023-07-27

Similar Documents

Publication Publication Date Title
CA2770457C (fr) Adhesif thermofusible a basse temperature d'application
CA2832601C (fr) Adhesif thermofusible a base de polyolefine et qui contient un plastifiant solide
CA2918015C (fr) Adhesif thermofusible comportant un copolymere sequence styrenique hydrogene et un copolymere d'ethylene acetate de vinyle presentant une force de blocage faible
JP5850683B2 (ja) ホットメルト接着剤
JP5947153B2 (ja) ホットメルト接着剤
RU2660860C2 (ru) Эластичный присоединяющий клей и его применение
US20060142447A1 (en) Methods for releasably attaching substrates using hot melt pressure sensitive adhesives
JP5192121B2 (ja) 低適用温度ホットメルト接着剤
KR20170118751A (ko) 핫 멜트 접착제 및 일회용 제품
CN113853415B (zh) 包含苯乙烯嵌段共聚物和蜡的热熔融组合物
JP7108035B2 (ja) ホットメルト接着剤組成物
EP3994220A1 (fr) Adhésifs sensibles à la pression thermofusibles à faible pégosité
EP4157937A1 (fr) Composition d'adhésif thermofusible ayant une résistance améliorée au mouillé
JP2023506847A (ja) ホットメルト接着剤組成物
EP4185257A1 (fr) Composition adhésive thermofusible
EP4186956A1 (fr) Composition adhésive thermofusible
KR20210104102A (ko) 일회용 부직포 위생 제품의 구성을 위한 신규 핫멜트 접착제

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20221123

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA